CN108998688A - A kind of nano-porous gold material and preparation method - Google Patents
A kind of nano-porous gold material and preparation method Download PDFInfo
- Publication number
- CN108998688A CN108998688A CN201810740995.3A CN201810740995A CN108998688A CN 108998688 A CN108998688 A CN 108998688A CN 201810740995 A CN201810740995 A CN 201810740995A CN 108998688 A CN108998688 A CN 108998688A
- Authority
- CN
- China
- Prior art keywords
- preparation
- silver
- nano
- porous gold
- billon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/08—Alloys with open or closed pores
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/02—Alloys based on gold
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
- Catalysts (AREA)
- ing And Chemical Polishing (AREA)
Abstract
The invention belongs to field of nanometer material technology, a kind of nano-porous gold material and preparation method are disclosed, which includes: that (1) takes and carries out surface polishing and cleaning treatment with a thickness of the silver-colored billon of 0.8-4.0mm；(2) the silver-colored billon after step (1) polishing cleaning is placed in stainless steel clamping plate, is rolled in milling train, until the silver-colored billon amounts of thickness variation is 50%-98%, equivalent strain amount is 0.8-4.52；(3) under inert gas shielding, the silver-colored billon that step (3) obtains is heat-treated 1-5h at 870-950 DEG C；(4) the silver-colored billon after heat treatment is immersed in strong acid and freely corrodes 2-9h, with washes of absolute alcohol and drying after taking-up, the nano-porous gold material is made.Present invention process is simple, of less demanding to raw material, using free etch, the nano-porous gold material ligament of preparation and aperture is respectively less than 20nm and structure is uniform.
Description
Technical field
The invention belongs to field of nanometer material technology, more particularly, to a kind of nano-porous gold material and preparation method.
Background technique
Nano porous metal refers to porous metal material of the aperture size in nanometer range, by continuous ligament and hole group
At the porous structure of the three-dimensional co-continuous of formation.Nano porous metal is with high porosity, the nanometer with big internal surface area
Hole, is a kind of new function material for having both function and structure double attribute, existing high conductivity, solderability, high-termal conductivity,
The excellent properties of the metal materials such as anticorrosive, antifatigue, ductility and structural strength height, high temperature resistant, and there is nano material
Skin effect and dimensional effect.
Nano porous metal material can be widely applied to biology, medicine, electronics, optics, catalysis, sensor and biology point
The fields such as the isolation and purification of son, it is this to have a variety of advantages, high-precision, the preparation of the nano porous metal of big flux, application
And products thereof production have become it is current both at home and abroad to the popular problem of porous material research.Noble metal porous material catalysis,
The various aspects such as medium transmission, porous electrode, biosensor technique and energy storage, which have had, to be widely applied, and expensive
In metal, nano-porous gold is again receive more and more attention by feat of excellent properties such as better stability, ductility,
The research of nano-porous gold is especially prepared to Ag-Au alloy removal alloying.
The currently used method for preparing nano-porous gold has template and removal alloying method.Template refers to one kind
The material of nano-porous structure is had been provided with as template, is deposited to target metal materials by either physically or chemically more
In the hole of hole template, removing template then is removed by modes such as annealing, sintering, etching or dissolutions, prepares nano porous metal.It goes
Alloying, which is broadly divided into, freely to be corroded and two kinds of electrochemical corrosion.Freely corrode to be called and do chemical attack, refers to that alloy is direct
The process that selective corrosion occurs is contacted with etchant solution, corrosion reaction acts directly on alloy.Electrochemical corrosion is with gold
Category alloy is working electrode, and platinum electrode and saturated calomel electrode are that electrode and reference electrode are pressurizeed on the working electrode (s, made
Element dissolution more active in metal alloy is obtained in the electrolyte, to form nano porous metal.In above-mentioned preparation method,
Template complex process, higher cost are not suitable for industrial production.Although electrochemical erosion method is easier to obtain ligament and aperture
Smaller nano porous metal, but be more difficult in experimental implementation than free etch more complicated.
Experiment at present, which shows freely to corrode, can prepare ligament and aperture size as the nanoporous of 6nm-60nm or so
Metal, and reducing the ligament of porous material and aperture size effectively can increase specific surface area, obtain superior performance.Mesh
The nano porous metal of preceding preparation small size has harsh requirement, such as film or amorphous alloy to presoma.Yi
Ding et al. (Ding Y, Kim Y J, Erlebacher J.Nanoporous Gold Leaf: " Ancient
Technology "/Advanced Material [J] Advanced Materials, 2004,16 (21): 1897-1900.)
Nano-porous gold of the ligament having a size of 6nm is prepared using the method freely corroded, but the preparation process of its presoma is very multiple
It is miscellaneous, it needs by repeatedly beating the platinum leaf obtained with a thickness of 100nm." a kind of superfine nano disclosed in CN104928518A
Porous metals and preparation method thereof " are immersed in the corrosion such as unsaturated carbonate solution by will get rid of the amorphous alloy ribbon with method preparation
Freely corroding in liquid can get the nano porous metal that characteristic size is less than 10nm.But presoma alloy needed for this method
For amorphous alloy, preparation process complexity." a kind of preparation method of nano-porous gold " disclosed in CN101787458A, by will be golden
Silver alloy paillon immerses in the metal cation containing high-valence state and halide anion solution, is utilizing ammonium hydroxide, thiosulfuric acid
The nano-porous gold that aperture is 2nm-100nm has been made in the silver halide that the removals such as sodium generate.But its alloy foil sheet used is thick
Degree is 100nm, expensive, and preparation is difficult.And a kind of " electrum nano porous metal material disclosed in CN103103571A
Material and its preparation process " is prepared for the porous gold that aperture is 15 ± 2nm, but it is by the way of electrochemical corrosion, and before corroding
Cold rolling in flakes and long term annealing is in order to obtain with a thickness of 25 μm of presoma alloy, and its annealing time is longer, needs
20h。
Summary of the invention
In order to overcome drawbacks described above, the present invention provides a kind of simple process, of less demanding to raw material, using free corruption
The preparation of erosion method, ligament and aperture are respectively less than the method for the uniform nano-porous gold material of 20nm, structure and utilize the method system
Standby nano-porous gold material.
One aspect of the present invention provides a kind of preparation method of nano-porous gold material, which includes:
(1) it takes and carries out surface polishing and cleaning treatment with a thickness of the silver-colored billon of 0.8-4.0mm；
(2) the silver-colored billon after step (1) polishing cleaning is placed in stainless steel clamping plate, is rolled in milling train, until
The silver billon amounts of thickness variation is 50%-98%, and equivalent strain amount is 0.8-4.52；
(3) under inert gas shielding, the silver-colored billon that step (2) obtains is heat-treated 1-5h at 870-950 DEG C；
(4) the silver-colored billon after heat treatment is immersed in strong acid and freely corrodes 2-9h, after taking-up simultaneously with washes of absolute alcohol
It is dry, the nano-porous gold material is made.
Wherein, the calculation of alloy amounts of thickness variation is that equivalent strain calculation is h in step (2)0And h1Point
Not Wei sample original depth and final thickness.
Surface polishing and cleaning treatment are being carried out to silver-colored billon, after removing oxide on surface and organic matter, then to its into
Row rolling, the crystal grain refinement of silver-colored billon is made by the plastic deformation generated in the operation of rolling, and intra-die generates a large amount of positions
Mistake, distortion of lattice aggravation, then make alloy that reply and a small amount of recrystallization occur by heat treatment, dislocation density is reduced, formation is uniform
Tiny crystal grain, be conducive to that silver-colored billon forms ligament after freely corroding and aperture size is smaller in this way, structure is more equal
Even nano-porous gold material.Heat treatment time 1-5h is preferred, unsuitable too long, to prevent silver-colored billon from recrystallization and crystalline substance occurs
Grain length is big, is roughened the nano-porous gold structure obtained after freely corroding.Ag atom and strong acid occur in free corrosion process
Chemical reaction is gradually dissolved, and Au atom diffuses to form rich golden skeleton, ultimately forms nano-porous structure.
In accordance with the present invention it is preferred that in step (1), the silver billon is commercial cast alloy, using vacuum melting,
Purity is 99.99% or more, and wherein the mass ratio of Ag and Au is 4:1-1:1.
In accordance with the present invention it is preferred that further including being closed to the silver gold after heat treatment before step (4) after step (3)
Gold carries out surface polishing, cleaning treatment and drying.
In accordance with the present invention it is preferred that the step of cleaning treatment includes: to be cleaned by ultrasonic in dehydrated alcohol, when cleaning
Between be 3-5min.
In accordance with the present invention it is preferred that in step (2), the stainless steel clamping plate be two panels with a thickness of 0.4-0.6mm not
Become rusty steel plate.
In accordance with the present invention it is preferred that the two initial spacing of roll spacing in milling train are 1.8-5.0mm in step (2), roll
It is constantly regulate in system and pricks roller spacing, rolled the two rolls spacing every time and reduce 0.1-0.2mm, milling train revolving speed is 30-40r/
mim。
In accordance with the present invention it is preferred that the inert gas is argon gas in step (3).
In accordance with the present invention it is preferred that the strong acid is the concentrated nitric acid of concentration 65%-68% in step (4).
Another aspect of the present invention, which provides, a kind of utilizes nano-porous gold material made from the above method, the nanoporous
The aperture of golden material and ligament size are respectively less than 20nm, are more than or equal to 8nm.
Nano-porous gold material disclosed in the present invention is by carrying out rolling deformation and the heat treatment of short time to alloy
Carry out refining alloy crystal grain, makes that it obtains aperture after freely corroding and ligament characteristic size is respectively less than 20nm, structure is uniformly received
Meter Duo Kong gold material, and wherein smallest size of ligament and aperture up to 8nm.
Compared with prior art, the present invention has the advantage that
1, the present invention requires presoma alloy low, without preparing alloy firm or the amorphous conjunction with a thickness of Nano grade
Gold, and preparation method is simple, laboratory equipment is easy to get.
2, the present invention is using the method freely corroded, and easy to operate, process costs are low, and experiment condition is easy to control.
3, the present invention is by the pre-treatment to alloy progress rolling deformation and the heat treatment of short time, after freely corroding
It can be obtained ligament and aperture be respectively less than 20nm, the nano-porous gold material more than or equal to 8nm.
Other features and advantages of the present invention will then part of the detailed description can be specified.
Detailed description of the invention
Exemplary embodiment of the invention is described in more detail in conjunction with the accompanying drawings, it is of the invention above-mentioned and
Other purposes, feature and advantage will be apparent, wherein identical with reference to mark in exemplary embodiment of the invention
Number typically represent same parts.
Fig. 1 shows the electron scanning micrograph of the nano-porous gold material of the embodiment of the present invention 1.
Fig. 2 shows the electron scanning micrographs of the nano-porous gold material of the embodiment of the present invention 2.
Specific embodiment
The preferred embodiment of the present invention is described in more detail below.Although the following describe preferred realities of the invention
Mode is applied, however, it is to be appreciated that may be realized in various forms the present invention without that should be limited by embodiments set forth herein
System.
Embodiment 1
Prepare the more empty golden materials of nanometer as shown in Figure 1:
It will be purity be 99.99%, mass ratio Ag:Au=7:3, the Ag having a size of 7 × 7 × 1mm70Au30Alloy is first
It is surface-treated, with 400# sand paper polishing sample surfaces, removes oxide and other spots, be put into equipped with dehydrated alcohol
It is cleaned by ultrasonic 3 minutes in beaker, obtains clean alloy.
The Ag that will be handled well70Au30Alloy is clipped in two panels with a thickness of in the stainless steel plate of 0.5mm, and the stainless steel plate is by one
Sheet material doubling rolls, and is then sent between two roll of milling train and is rolled, by sample taking-up vernier calliper after rolling
Ruler measures thickness.By repeatedly adjusting roll spacing, until the amounts of thickness variation of alloy reaches requirement.During the rolling
The revolving speed of milling train is 35r/min, adjusts two roll spacing using thin bud screw rod, and initial spacing is 2mm, rolls spacing every time and subtracts
Few 0.2mm, until the amounts of thickness variation of alloy reaches 60%, equivalent strain value reaches 1.06.
Deformed alloy is placed in tube furnace and keeps the temperature 3h under conditions of 900 DEG C, argon gas is led in insulating process to be prevented
It is aoxidized.Oxide and other spots are removed, are put into equipped with anhydrous with 400# sand paper polishing sample surfaces again after heat treatment
It is cleaned by ultrasonic 3 minutes in the beaker of ethyl alcohol, alloy is immersed in the concentrated nitric acid that concentration is 65%~68% after dry and is freely corroded
It is taken out after 7h, it is sample wash is clean, dry with dehydrated alcohol, obtain nano-porous gold material.
Empty golden material, is mutually passed through as shown in Figure 1, sample forms more than the nanometer made from scanning electron microscope observation
Logical continuous and uniform nano-porous gold structure, the average-size for being computed the sample ligament and aperture are each about 8nm.
Embodiment 2
Prepare the more empty golden materials of nanometer as shown in Figure 2:
Preparation method and implementation 1 are consistent, and there is only following differences: amounts of thickness variation 98%, equivalent strain value are
4.52, free etching time is 3h.
Empty golden material, is mutually passed through as shown in Fig. 2, sample forms more than the nanometer made from scanning electron microscope observation
Logical continuous and uniform nano-porous gold structure, the average-size for being computed the sample ligament is about 13nm, and aperture is averaged
Size is about 12nm.
Embodiment 3
Preparation method and implementation 1 are consistent, and there is only following differences: amounts of thickness variation 90%, equivalent strain value are
2.66, free etching time is 7h.
Observe empty golden material more than nanometer obtained with scanning electron microscope, sample form be mutually communicated continuous and
Uniform nano-porous gold structure, the average-size for being computed the sample ligament is about 12.9nm, and the average-size in aperture is about
11.5nm。
Comparative example 1
Preparation method and embodiment 1 are consistent, and there is only following differences: without rolling and being heat-treated.
Observe empty golden material more than nanometer obtained with scanning electron microscope, sample form be mutually communicated continuous and
Uniform nano-porous gold structure, the average-size for being computed the sample ligament is about 21.2nm, and the average-size in aperture is about
24.7nm。
Various embodiments of the present invention are described above, above description is exemplary, and non-exclusive, and
It is also not necessarily limited to disclosed each embodiment.Without departing from the scope and spirit of illustrated each embodiment, for this
Many modifications and changes are obvious for the those of ordinary skill of technical field.
Claims (9)
1. a kind of preparation method of nano-porous gold material, which is characterized in that the preparation method includes:
(1) it takes and carries out surface polishing and cleaning treatment with a thickness of the silver-colored billon thin slice of 0.8-4.0mm；
(2) the silver-colored billon after step (1) polishing cleaning is placed in stainless steel clamping plate, is rolled in milling train, until described
Silver-colored billon amounts of thickness variation is 50%-98%, and equivalent strain amount is 0.8-4.52；
(3) under inert gas shielding, the silver-colored billon that step (2) obtains is heat-treated 1-5h at 870-950 DEG C；
(4) silver-colored billon after heat treatment is immersed in strong acid and freely corrodes 2-9h, with washes of absolute alcohol and drying after taking-up,
The nano-porous gold material is made.
2. preparation method according to claim 1, which is characterized in that in step (1), the silver billon is commercial as cast condition
Alloy, using vacuum melting, purity is 99.99% or more, and wherein the mass ratio of Ag and Au is 4:1-1:1.
3. preparation method according to claim 1, which is characterized in that after step (3), before step (4), further include
Surface polishing, cleaning treatment and drying are carried out to the silver-colored billon after heat treatment.
4. preparation method according to claim 1 or 3, which is characterized in that the step of cleaning treatment includes: anhydrous
It is cleaned by ultrasonic in ethyl alcohol, scavenging period 3-5min.
5. preparation method according to claim 1, which is characterized in that in step (2), the stainless steel clamping plate is that two panels is thick
Degree is the stainless steel plate of 0.4-0.6mm.
6. preparation method according to claim 1, which is characterized in that in step (2), two roll spacing in milling train are initial
Spacing is 1.8-5.0mm, constantly regulate in rolling and pricks roller spacing, rolls the two rolls spacing every time and reduces 0.1-0.2mm, rolls
Machine revolving speed is 30-40r/mim.
7. preparation method according to claim 1, which is characterized in that in step (3), the inert gas is argon gas.
8. preparation method according to claim 1, which is characterized in that in step (4), the strong acid is concentration 65%-
68% concentrated nitric acid.
9. nano-porous gold material made from the preparation method as described in any one of claim 1-8, which is characterized in that institute
The aperture and ligament size for stating nano-porous gold material are respectively less than 20nm, are more than or equal to 8nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810740995.3A CN108998688B (en) | 2018-07-08 | 2018-07-08 | Nano-porous gold material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810740995.3A CN108998688B (en) | 2018-07-08 | 2018-07-08 | Nano-porous gold material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108998688A true CN108998688A (en) | 2018-12-14 |
| CN108998688B CN108998688B (en) | 2020-01-03 |
Family
ID=64598540
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810740995.3A Active CN108998688B (en) | 2018-07-08 | 2018-07-08 | Nano-porous gold material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108998688B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103103571A (en) * | 2012-11-13 | 2013-05-15 | 苏州谷力生物科技有限公司 | Gold-silver alloy nano porous metal material and preparation technology thereof |
| CN103774149A (en) * | 2014-02-10 | 2014-05-07 | 天津工业大学 | Preparation method of high-strength nano-porous nickel film |
| CN104528803A (en) * | 2014-12-24 | 2015-04-22 | 西安理工大学 | Preparation method of ZnO flaky porous nanometer material |
| CN105063400A (en) * | 2015-09-16 | 2015-11-18 | 哈尔滨工业大学 | Preparation method for nanometer porous titanium |
| CN105220012A (en) * | 2015-10-29 | 2016-01-06 | 无锡桥阳机械制造有限公司 | A kind of preparation of nano porous metal material |
-
2018
- 2018-07-08 CN CN201810740995.3A patent/CN108998688B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103103571A (en) * | 2012-11-13 | 2013-05-15 | 苏州谷力生物科技有限公司 | Gold-silver alloy nano porous metal material and preparation technology thereof |
| CN103774149A (en) * | 2014-02-10 | 2014-05-07 | 天津工业大学 | Preparation method of high-strength nano-porous nickel film |
| CN104528803A (en) * | 2014-12-24 | 2015-04-22 | 西安理工大学 | Preparation method of ZnO flaky porous nanometer material |
| CN105063400A (en) * | 2015-09-16 | 2015-11-18 | 哈尔滨工业大学 | Preparation method for nanometer porous titanium |
| CN105220012A (en) * | 2015-10-29 | 2016-01-06 | 无锡桥阳机械制造有限公司 | A kind of preparation of nano porous metal material |
Non-Patent Citations (2)
| Title |
|---|
| HANYU HUI ET AL.: "Effects of Cold Rolling and Annealing Prior to", 《NANOMATERIALS》 * |
| 印会鸣: "脱合金法制备纳米多孔金属和金属氧化物及其催化性能研究", 《中国博士学位论文全文数据库工程科技Ⅰ辑》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108998688B (en) | 2020-01-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Bayansal et al. | Nano-structured CuO films prepared by simple solution methods: plate-like, needle-like and network-like architectures | |
| CN101514407A (en) | Method for preparing nano porous gold | |
| CN101559492B (en) | Preparation method of metal nanometer line with controllable size | |
| CN100557083C (en) | A kind of transplantable ultrathin nano-porous gold film and preparation method thereof | |
| JP2014136832A (en) | Anodic oxide film and method for manufacturing the same | |
| CN101429680A (en) | Production method for direct growth of one-dimensional nano cuprous oxide array on metallic copper substrate | |
| CN103173795A (en) | Electroplating method | |
| CN101851771A (en) | Ordered porous alumina template capable of being directly used in electrochemical deposition and production method | |
| CN101838835A (en) | Ordered porous alumina template capable of being directly applied to electrochemical deposition and preparation method thereof | |
| CN101984145A (en) | Method for preparing two-way porous aluminium oxide template with adjustable aperture | |
| CN106676619B (en) | A kind of preparation method of glassy metal nano-porous structure | |
| Elsanousi et al. | Self-organized TiO 2 nanotubes with controlled dimensions by anodic oxidation | |
| CN100381235C (en) | Method for preparing nickel phosphor alloy nanowire | |
| CN104357886A (en) | Method for chemically depositing diffused tin-zinc crystal nucleus on surface of high-purity aluminum foil for medium/high-voltage positive electrode | |
| CN104733181A (en) | Method and device for depositing disperse tin and zinc crystal nucleuses on surface of highly pure aluminum foil for medium and high voltage anodes in mist spraying mode | |
| CN101597775A (en) | A kind of nanoporous gold electrochemical preparation method | |
| CN100543191C (en) | A kind of preparation method of nanostructure dimensional stable anode | |
| CN107749350B (en) | A kind of super capacitor cupro-nickel combination electrode and its preparation process | |
| CN108998688A (en) | A kind of nano-porous gold material and preparation method | |
| CN103774193A (en) | Method for electrolytic-depositing dispersed zinc crystal nucleuses on surface of medium-high voltage electronic aluminum foil | |
| CN107089664B (en) | Preparation method of nano porous silicon material | |
| Cao et al. | Designing micro-nano structure of anodized iron oxide films by metallographic adjustment on T8 steel | |
| Bloom et al. | Steel Corrosion Mechanisms: The Growth and Breakdown of Protective Films in High‐Temperature Aqueous Systems: at 316° C | |
| CN114703529B (en) | Magnesium alloy with super-hydrophobic MAO-LDH composite membrane layer and preparation method thereof | |
| CN105734335B (en) | A kind of copper-based nano porous membrane and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |